JP4927709B2 - Coated laminate comprising a layer of barrier coating - Google Patents

Description

  The present invention relates to multilayer functional coatings, in particular such coatings comprising at least one barrier coating layer.

REFERENCE RELATED APPLICATION This application is a U.S. patent application serial no. US Patent Application Serial No. 10 / 007,382, filed April 25, 2002, which is a CIP. US Patent Application Serial No. 10 / 133,805, filed March 25, 2003, which is a CIP. No. 10 / 397,001 CIP filed April 24, 2003, US Patent Application Serial No. 10 / 422,095 CIP. This application is a provisional application for Serial No. Serial No. Serial No. It also claims a 60 / 376,000 interest. All of these applications are hereby incorporated by reference in their entirety.

  Substrates such as glass are used in many applications ranging from commercial buildings to homes, automobiles, machinery and the like. These substrates are often coated with a functional coating to obtain the desired performance characteristics.

  A wide variety of functional coatings are known in the art, including, but not limited to, conductive coatings, solar control coatings, photocatalytic coatings, low emission coatings, transparent conductive coatings, etc. . An example of a functional coating is a metal-based high transmittance, low radiation coating that includes at least one metal layer (s) sandwiched between layers of dielectric material. Usually the metal layer is gold, copper or silver and the dielectric material is a metal oxide such as tin oxide, indium oxide, titanium oxide, bismuth oxide, zinc oxide, zirconium oxide, or zinc / tin oxide. is there.

  For some applications, it is necessary to heat the substrate coated with the functional coating. For example, a coated glass substrate used as an automotive windshield may need to be heated to bend the glass. Typically, the glass will be heated to a maximum temperature of 1150 ° F to 1200 ° F for 20-30 minutes to achieve the curvature required for automotive windshields. Due to the complexity of the curvature, the temperature will be longer and the time will be longer.

  Heating the coated substrate can be problematic if the coating includes a layer or layers that are subject to degradation by heating. In general, heating of a coated substrate will produce advantageous results up to a certain temperature (for a certain period of time) for various reasons, for example, by which the mobile substance is easily moved by heating and flows out of a certain coating layer. Deaf, but still bad. The combination of the temperature at which the coating layer can be heated before the performance of the coating begins to deteriorate and the exposure time is referred to herein as the “heat budget” of the coating. The performance of the coating begins to deteriorate after its critical heat is exceeded. This is because at least one coating layer begins to deteriorate. Every coating layer in a coating laminate has a critical heat quantity that varies depending on the material used to form the coating. The critical amount of heat for a coated laminate is determined by the coating layer having the lowest critical amount of heat in the laminate, where it begins to degrade.

  For example, in a high transmittance, low radiation coating as described above, the metal layer (s) typically have the lowest critical heat in the coating stack. When a glass substrate coated with such a coating is exposed to the heating conditions typically associated with bending, eg, 1150 ° F. to 1200 ° F. for 20-30 minutes, the metal layer (s) deteriorate. Will do. Degradation of the metal layer (s) can result in a coated substrate with reduced optical and / or solar control properties. In particular, functional coatings may exhibit increased electrical resistance, increased haze, decreased solar infrared (IR) reflectivity, decreased visible light transmission, increased radiation, and the like.

  In addition to heating, functional coatings with other things such as, but not limited to, exposure to certain chemicals including salts, chlorides, sulfur, chlorine, alkalis, and halogens such as enamel May cause deterioration of the inner layer.

  In order to ensure optimum performance of the coated substrate, any degradable coating layer (s) in the coated laminate will result in degradation of the coating layer and subsequently reduce the performance of the coated substrate. Protection from unfavorable conditions and / or substances. Conventionally, a sacrificial layer (also known as a “blocker layer”), such as an underlayer, is added to a coating laminate, eg, a metal-based high transmittance, low radiation coating. Or have been applied to thicker levels to protect the degradable layer (s). The sacrificial layer preferentially responds to or reacts to undesirable conditions and protects other selected layers in the coating laminate. The problem with adding underlayer (s) or using a thicker underlayer (s) is that after heating the coating, excess underlayer damage at the interface of the individual layers of the coating Can result in poor adhesion and increased haze. In addition, excess substrate may soften the coating and be easily damaged by rubbing.

  The present invention provides a coating composition having at least one barrier coating layer for protecting any degradable layer (s) in the coating laminate. The coating structure according to the present invention exhibits an increased critical heat and an improved ability to withstand chemical corrosion.

In one non-limiting embodiment, the present invention resides in a coating structure comprising at least one degradable layer and at least one barrier coating layer, wherein the barrier coating layer is 10 g / m at a temperature of 900 ° F. ^It has an oxygen transmission rate of ² / day or less.

In another non-limiting embodiment, the present invention resides in a coated substrate having a coating structure comprising at least one degradable layer and at least one barrier layer applied over at least a portion of the substrate, wherein the barrier The coating layer has an oxygen transmission rate of 10 g / m ² / day or less at a temperature of 900 ° F.

In another non-limiting embodiment, the present invention is directed to a method of forming a multilayer coated substrate comprising applying a degradable coating layer over the substrate and applying a barrier coating layer over the degradable coating layer. Yes, in this case, the barrier coating layer has an oxygen transmission rate of 10 g / m ² / day or less at a temperature of 900 ° F.

DESCRIPTION OF THE INVENTION As used herein, “left”, “right”, “inner”, “outer”, “above”, “below”, “one” Spatial or directional terms such as “top”, “bottom”, etc. are understood to encompass a variety of alternative configurations, and thus such terms are limiting. Should not be considered as.

  Furthermore, all numbers used herein to express size, physical characteristics, processing parameters, component amounts, reaction conditions, etc. used in the specification and claims are in any case. It should be understood that it can be modified by the term “about”. Accordingly, unless stated to the contrary, the numerical values set forth in the following specification and claims can be varied depending upon the desired properties sought to be obtained by the present invention. . At the very least, it is not intended to limit the application of the doctrine of equivalents to the claims, but each number refers to a number of reported significant numbers and applies the usual rounding method. Should be considered to have been obtained. Further, it should be understood that many of the ranges described herein are inclusive of any small ranges contained therein, including initial and final range values. For example, the range described as “1-10” should be considered to encompass any small range that falls between the minimum value of 1 and the maximum value of 10 (including those values). . That is, all subranges that start with a minimum value of 1 or more and end with a maximum value of 10 or less, such as 1.0 to 3.8, 6.6 to 9.7, and 5.5 to 10.0. A range is included.

  The terms used here are “on”, “applied on / over”, “formed on / over” , “Deposited on / over”, “overlay” and “provided on / over” , Above, but not necessarily in contact with the surface. For example, a coating layer “formed over” a substrate excludes the presence of one or more other coating layers of the same or different composition located between the formed coating layer and the substrate. is not. For example, the substrate (eg, glass or ceramic) can include conventional coatings, such as coatings known in the field of coating substrates.

  The present invention relates to a coating structure comprising at least one barrier coating layer and at least one coating layer that is susceptible to degradation upon exposure to certain conditions such as, but not limited to, thermal and chemical erosion. It is in. A coating layer that is susceptible to degradation is referred to herein as a “degradable layer”.

The barrier coating layer according to the present invention may be a single layer or a plurality of coating layers. The barrier coating layer can act as a barrier to various materials such as, but not limited to oxygen, copper, halides, sulfides, sulfur, alkalis, water, and the like. The barrier coating layer of the present invention is substantially stable, substantially non-consumable, and substantially non-reactive. Substantially stable, substantially non-consumable, and substantially non-reactive means that the stoichiometric ratio of component to O ₂ in the barrier layer varies by more than ± 5%. Means no. Regardless of the conditions to which the barrier coating layer is exposed, it will maintain substantially the same configuration. For example, in the case of an oxygen barrier coating, once the barrier coating layer begins to be fully oxidized, it will remain fully oxidized regardless of the conditions.

According to the present invention, when the barrier coating layer protects the degradable layer from oxygen, the barrier coating layer has a low permeability to oxygen. As a non-limiting embodiment of the present invention, the barrier coating layer has an oxygen transmission rate of 900 g / m ² / day or less, such as 8 g / m ² / day or less, or 5 g / m ² / day or less. Indicates the rate.

  Next, it will be illustrated how the oxygen permeability can be measured. Three transparent glasses were coated with a 1400 厚 thick first barrier layer containing an alloy of alumina and silica (60 wt% alumina and 40 wt% silica). Next, a coating comprising a 114 チ タ ン titanium layer was applied over the alumina / silica alloy layer. Finally, the samples were coated with a second barrier coating layer comprising an alloy of alumina and silica (60 wt% alumina and 40 wt% silica). The thickness of the second barrier layer was different for each sample. One sample (Sample A) had a second barrier layer having a thickness of 266 mm. Another sample (Sample B) had a second barrier coating layer having a thickness of 515 mm. The last sample (Sample C) had a second barrier layer having a thickness of 1071 mm. Initially, all samples appeared dark on the transmission side as a result of absorption by the titanium layer.

After preparing the samples, each sample was heated to 1300 ° F. The length of time it took for the sample to become transparent (no absorption) was recorded. When the sample became transparent, it indicated that the initially deposited titanium was completely oxidized and became titania. Sample A took 80 minutes to fully oxidize. Sample B took 115 minutes to fully oxidize. Sample C took 130 minutes to be completely oxidized. Using the recorded “oxidation” time, the transmittance (P) was calculated by the following formula:
P = T / 10E ⁸ [Å / cm] × 4.5 [g / cm ³ ] × 10E4 [cm ² / m ² ] /47.9 [g / mol] × 32 [g / mol] / R × 1440 [Minutes / day]
Where
T = thickness of titanium layer [Å];
4.5 g / cm ³ = density of titanium;
47.9 g / mol = atomic weight of titanium;
32 g / mol = molecular weight of O ₂ ; and R = recorded oxidation time (minutes).

The transmittance of Sample A was 0.6 g / m ² / day by calculation. The transmittance of Sample B was 0.4 g / m ² / day by calculation. The transmittance of Sample C was 0.4 g / m ² / day by calculation.

  According to the invention, the barrier coating layer can have a refractive index equal to any value at 550 nm. If the barrier coating consists of multiple layers, the refractive index of all barrier coatings can be calculated using standard methods well known in the art. As a non-limiting embodiment, the entire barrier coating layer has a refractive index equal to or less than 3, for example, a refractive index of 2.5 or lower, or 1.8 or lower.

  As a non-limiting embodiment of the present invention, the barrier coating layer is a layer composed of one or more metal oxide materials such as, but not limited to, alumina, silica, or mixtures thereof. It is. For example, the barrier coating layer may be made of all alumina or all silica. In another non-limiting embodiment, the barrier coating layer is a combination of alumina and silica, such as 5 wt% to 95 wt% alumina and 95 wt% to 5 wt% silica, or 10 wt% to 90 wt%. % Alumina and 90% to 10% silica, or 15% to 90% alumina and 85% to 10% silica, or 50% to 75% alumina and 50% by weight. % To 25% by weight silica, (but not limited to).

  As a non-limiting embodiment of the present invention, the barrier coating layer comprises a single layer, and the composition of the barrier coating varies throughout. For example, the barrier coating composition can be composed of two materials, a first material and a second material. The barrier coating layer is on the substrate, the concentration of the first material of the barrier coating being maximum near the substrate, and the concentration of the second material of the barrier coating increases, for example, gradually as the distance from the substrate increases. Apply in an increasing manner. The composition of the barrier coating farthest from the substrate has the highest concentration of the second material. As another non-limiting embodiment of the invention, the barrier coating is a single layer and the composition of the barrier coating is generally uniform throughout.

  As a non-limiting embodiment of the present invention, the thickness of the barrier coating layer can be in the range of up to 2μ (20,000 Å), for example, in the range of 50 Å to 5,400 Å, or 85 Å to 600 Å.

  As a non-limiting embodiment of the present invention when the barrier coating layer is comprised of a plurality of layers, the barrier coating is a first silica and / or alumina applied over a second layer of silica and / or alumina. Including layers. For example, the first layer can be alumina or a silica / alumina mixture comprising more than 5 wt% alumina, such as more than 10 wt% alumina, or more than 15 wt% alumina. The first layer can be up to 1 μ thick, for example, 50 to 400 mm, or 60 to 30 mm thick. The second layer can comprise a silica / alumina mixture comprising greater than 40 wt% silica, such as greater than 50 wt% silica, or greater than 60 wt% silica. The second layer can have a thickness of up to 1 μm, for example, 50 to 5,000, or 60 to 300 mm. Each of the layers including the barrier coating layer may have a uniform composition or may have a composition that varies throughout.

  In accordance with the present invention, the barrier coating layer can be incorporated into any functional coating known in the art. As a non-limiting embodiment of the present invention, a barrier coating layer is incorporated into the metal-based coating structure. As used herein, a metal-based coating composition includes any coating that includes at least one metal layer. In particular, the barrier coating layer can be incorporated into a metal-based coating structure that includes one or more layers of the metal-based coating laminate unit described in detail below. The metal-based laminate unit can be repeated any number of times to produce a cascaded composition that is well known in the art.

  The metal-based coated laminate unit includes a first layer of dielectric material, a layer of electromagnetic wave reflecting material, an underlayer, and a second layer of dielectric material. The first layer of dielectric material can be composed of a metal oxide or metal alloy oxide that is transparent to visible light. Examples of suitable metal oxides include, but are not limited to indium oxide, titanium oxide, zinc oxide, tin oxide, and mixtures and alloys thereof (eg, zinc stannate). For example, the first layer of dielectric material comprises an alloy of zinc and tin in a proportion ranging from 10 to 90 wt% zinc, such as 30 to 60 wt% zinc, or 46 to 50 wt% zinc. be able to. As another example, the first layer of dielectric material can be composed of multiple layers, for example, one layer of zinc stannate and another layer of zinc oxide. Suitable first layers of dielectric material are described in US Pat. Nos. 4,610,771 and 5,821,001, which are hereby incorporated by reference.

  The thickness of the first layer of dielectric material can be in the range of 100 to 800 inches, such as 200 to 750 inches, or 280 to 700 inches.

  A layer of electromagnetic wave reflective material is applied over at least a portion of the first layer of dielectric material. The electromagnetic wave reflective material can reflect in the solar infrared region, the thermal infrared region, and / or the microwave region. The electromagnetic wave reflective material can include a metal such as gold, copper, or silver. The electromagnetic wave reflective material can include not only a combination of the above-described metals but also an alloy thereof. In the described metal-based coated laminate unit, the layer of the electromagnetic wave reflecting material is a degrading layer.

  The thickness of the layer of the electromagnetic wave reflecting material can be in the range of 50 to 300 mm, for example, 60 to 200 mm, or 70 to 150 mm.

  An underlayer is applied over at least a portion of the layer of electromagnetic wave reflecting material. The underlayer can be any material known in the art as a getter / collector material, i.e., a substance that readily absorbs gases. Suitable materials for the substrate include titanium, copper, aluminum, nickel, niobium, yttrium, zirconium, hafnium, chromium, and alloys thereof; nickel-chromium alloy and cobalt-chromium alloy; indium tin suboxide, titanium suboxide And suboxides such as zinc aluminum suboxide; and nitrides such as silicon nitride, but are not limited thereto.

As a non-limiting embodiment of the present invention, the underlayer is converted from metal to oxide or from suboxide to oxide, for example, by exposure to an O ₂ containing plasma or as a result of heating in air. be able to. Even if a substrate loses its ability as a getter / collector over time, it does not affect its classification as a substrate. For example, a coated laminate according to the present invention can include an underlayer that is initially constructed from titanium metal. Over time, the titanium metal layer will absorb oxygen and the titanium metal will be converted to titania, ie TiO ₂ . Titania no longer reacts with oxygen. In such a case, the titania initially present in the coated laminate as titanium metal is considered the underlayer.

  The thickness of the underlayer can be up to 50 mm, for example, in the range of 5 mm to 35 mm, or 8 mm to 30 mm, or 10 mm to 18 mm.

  A second layer of dielectric material is applied over at least a portion of the underlying layer. Suitable materials for the second layer of dielectric material and applied layer thicknesses are as described above for the first layer of dielectric material.

  The barrier coating layer may be applied anywhere within the coating structure comprised of one or more metal-based coating laminate units described above. As a non-limiting embodiment of the present invention, the coating structure includes one metal-based coating laminate unit, and a barrier coating layer is applied over the second layer of dielectric material. As another non-limiting embodiment of the present invention, the coating structure applies a barrier coating layer over the first layer of dielectric material, including one metal-based coating laminate unit. In yet another non-limiting embodiment of the present invention, a barrier coating layer is applied over the substrate, and one metal-based coating laminate unit is applied over the barrier coating layer.

  As another non-limiting embodiment of the present invention, at least one barrier coating layer can be incorporated anywhere in the coating structure in which the metal-based coating laminate unit described above is repeated at least twice, such as 3 When repeated a number of times, the coated laminate comprises three layers of electromagnetic wave reflective material. As a special embodiment, the coating structure comprises three metal-based coating laminate units and the barrier coating layer is the last coating layer, i.e. it is the first of the dielectric material of the third metal-based coating laminate unit. Applied over at least a portion of the bilayer. As another special embodiment, two barrier coating layers are included as the barrier coating layers form the first and last layers of the coating laminate.

  As various non-limiting embodiments of the present invention, other coating layers composed of various materials can be applied over the barrier coating layer. This is especially the case when the barrier coating layer is the last coating layer of the coating laminate. In one non-limiting embodiment of the present invention, a layer of titanium metal is applied over the barrier coating layer. In another non-limiting embodiment, a layer of carbon is applied over the barrier coating layer. Applying a dark heat-absorbing coating layer such as carbon over the barrier coating layer can increase the heating rate of the coated substrate.

  As another non-limiting embodiment of the present invention, the barrier coating layer comprises at least the following layers: at least one layer of transparent conductive oxide, such as fluorine doped titanium oxide, indium tin oxide, or zinc aluminum oxide And at least one layer of conductive nitride, such as titanium nitride or zirconium nitride. The arrangement of the conductive nitride layer and the transparent conductive oxide layer is not critical. That is, a conductive nitride layer may be applied over at least a portion of the transparent conductive oxide layer, and vice versa. In this embodiment, the barrier coating layer can be the first and / or last coating in the laminate.

  In the coated laminate described above, the conductive nitride layer is a degradable layer.

  The thickness of the transparent conductive oxide layer can be in the range of 1 to 5,000, for example, 5 to 2,500. The thickness of the conductive nitride layer can range from 1 to 2,500 mm, such as from 5 to 1,000 mm, or from 10 to 500 mm.

In addition to the various coating constructions, the present invention encompasses methods for producing these coatings. In particular, the present invention includes a method for forming a multilayer coated substrate comprising applying a degradable coating layer over the substrate and applying a barrier coating layer over the degradable coating layer, wherein the barrier comprises The coating layer has an oxygen permeability of 10 g / m ² / day or less at a temperature of 900 ° F. The barrier coating layer may be the last layer of the coating laminate, or it may be placed in the coating laminate. As a non-limiting embodiment, the present invention further includes applying another coating layer over the degradable coating layer and then applying a barrier coating layer. As another non-limiting embodiment, the present invention further includes applying another barrier coating layer on the substrate and then applying a degradable coating layer.

  The various coating layers discussed above can be applied using conventional techniques such as chemical vapor deposition (CVD), spray pyrolysis, and magnetron sputter vacuum deposition (MSVD).

  Suitable CVD deposition methods are described in the following references which are hereby incorporated by reference: US Pat. Nos. 4,853,257, 4,971,843, 5,536,718, , 464,657, 5,599,387, and 5,948,131.

  Suitable spray pyrolysis deposition methods are described in the following documents which are hereby incorporated by reference: US Pat. Nos. 4,719,126, 4,719,127, 4,111,150, And 3,660,061 specification.

  Suitable MSVD deposition methods are described in the following references, incorporated herein by reference: US Pat. Nos. 4,379,040, 4,861,669, and 4,900,633. . As a non-limiting embodiment of the present invention using MSVD to deposit a barrier coating layer, a target comprising 60 wt% aluminum and 40 wt% silicon is sputtered to produce a mixture, alloy or combination of alumina and silica. A barrier coating layer can be deposited.

  The multilayer coating construction of the present invention can be applied on a variety of substrates. Examples of suitable substrates include plastic substrates (eg, acrylic polymers such as polyacrylates; polyalkyl methacrylates such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, etc .; polyurethanes; polycarbonates; polyethylene terephthalate (PET) , Polyalkyl terephthalates such as polypropylene terephthalate, polybutylene terephthalate, etc .; polysiloxane-containing polymers; or copolymers of monomers for producing them, or mixtures thereof]; steel, galvanized steel, stainless steel And metal substrates such as, but not limited to, aluminum; ceramic substrates; tile substrates; glass substrates; any mixtures or combinations thereof; Not to. For example, the substrate may be conventional colorless soda / lime / silica glass, ie “transparent glass”, or colored or otherwise colored glass, borosilicate glass, lead glass, tempered glass, non-tempered glass , Annealed glass, or heat strengthened glass. The glass can be of any type, for example, conventional float glass or flat glass, and any optical properties such as visible light transmission, ultraviolet transmission, infrared transmission, and / or total Any value of solar energy transmission may consist of any composition having them. Glass types suitable for the practice of the present invention include, for example, U.S. Pat. Nos. 4,746,347, 4,792,536, 5,240,886, 5,385,872, and Although described in US Pat. No. 5,393,593, it should not be considered as limited thereto.

  The substrate can be any thickness. In embodiments where the substrate is glass, the substrate is generally thicker for architectural applications than for automotive applications. As a non-limiting aspect for architectural applications, the substrate can be a glass having a thickness in the range of 1 mm to 20 mm, such as 1 mm to 10 mm, or 2 mm to 6 mm. As a non-limiting aspect for automotive applications, the substrate can be laminated automotive windshield or at least one glass in a side window, and the substrate can be up to 5.0 mm thick, for example up to 4.0 mm, or 3 It can be up to 0.0 mm, or up to 2.5 mm thick, or up to 2.1 mm thick.

  When the substrate is glass, the glass is disclosed in U.S. Pat. Nos. 3,083,551, 3,220,816, and 3,843,346, which are hereby incorporated by reference. ) Using conventional float methods. As a non-limiting embodiment of the present invention, the coating layer discussed herein can be applied to glass during float glass processing, for example, while supporting the glass over molten tin in a float bath. .

  As a non-limiting embodiment, the present invention includes the coated substrate described below. A first dielectric layer composed of zinc stannate is deposited on the substrate at a thickness of 250 to 490, such as 340 to 440 and / or 375 to 425. The first silver layer is deposited on the first dielectric layer at a thickness of 50 to 175, such as 60 to 125, or 67 to 90. The first titanium underlayer is deposited on the first silver layer at a thickness of 10 to 30 mm, for example, 12 to 25 mm, or 15 to 22 mm. The zinc stannate dielectric layer is deposited on the first underlayer at a thickness of 600 to 800 inches, such as 650 to 750 inches, or 675 to 725 inches. The second silver layer is deposited on the second dielectric layer at a thickness of 50 to 175, for example, 60 to 125, or 67 to 90. The second titanium underlayer is deposited on the second dielectric layer at a thickness of 10 to 30 mm, such as 12 to 25 mm, or 15 to 22 mm. The zinc stannate stannate dielectric layer is deposited on the second underlayer at a thickness of 290 to 490, such as 340 to 440, or 375 to 425. A barrier layer composed of a mixture, alloy, or combination of alumina and silica containing 60% by weight alumina and 40% by weight silicon over the third dielectric layer is 100 to 600 mm, for example 150 to 500 mm, Alternatively, it is deposited at a thickness of 175 to 400 mm. A titania layer having a thickness in the range of 100 to 600, such as 150 to 500, or 175 to 400 is deposited over the alumina / silica layer to provide additional durability to the coating.

  The coated substrate according to the invention can be used in various applications, for example automotive transparencys, automotive side windows, windshields, rear windows, sunroofs or moon roofs, and residential or commercial windows, gas, electricity and micro It can be used in insulating glass units for oven doors for wave ovens, but is not limited to them.

  Substrates coated with the coating according to the invention perform better than conventional coated substrates. For example, the substrate coated according to the present invention is generally for producing automotive windshields, even after heating it during product manufacture, in terms of electrical resistivity, haze, solar IR reflectivity, visible light transmittance, etc. It will have better performance even after the kind of heating associated with bending glass plates or strengthening glass sheets. This is because the degradable layer (s) remains intact. Also, if the barrier coating layer is the last coating layer in the coating laminate, the coated substrate according to the present invention can better withstand mechanical and / or chemical injury during handling, transportation and storage. Furthermore, the coated laminate has better mechanical durability, chemical durability, and thermal stability during use as a microwave oven door.

  The present invention also encompasses a method of forming a system enclosed within a multilayer coating by incorporating at least one barrier coating layer into the coating laminate. The barrier layer can be incorporated anywhere in the coating laminate, i.e. in the individual layers of the metal-based coating laminate unit and / or between the metal-based coating laminate units. An enclosed system refers to the area between two barrier coating layers or between one barrier coating layer and a substrate. Essentially no material can enter or leave the enclosed system. The material that can flow through the enclosure is defined by the transmittance described above.

The method of the present invention allows the interaction between the coating layers in the coating laminate to be manipulated so that only the desired interaction occurs. Other functional coating layers, or other materials such as O ₂ outside the enclosed system, are constrained from contacting or reacting with the layers in the enclosed system.

The method of the present invention is particularly advantageous when the coating laminate includes the layer (s) to be kept from exposure to certain materials. For example, a coated laminate may include a metal layer such as silver that may degrade if exposed to oxygen. In such a case, the method of the present invention may apply a barrier coating layer to the encapsulated area where there is no O ₂ around the metal layer, both below and above the metal layer, or over the metal layer. Can be used by forming a barrier coating layer on the substrate and using the substrate in front of the metal layer as another oxygen barrier layer.

  The following example demonstrates the advantages of the present invention. The substrate is coated with a multilayer coating construction comprising three basic laminates similar to the laminate described above. The coating laminate is formed by MSVD, and the total coating consists of three silver layers, four dielectric material layers (the second dielectric layer of the first base laminate, the first dielectric layer of the second base laminate, and Together, forming one dielectric layer, combining the second dielectric layer of the second base laminate with the first dielectric base laminate of the third metal-based laminate unit, and another dielectric layer A body layer), and three underlayers. The dielectric material layer sandwiches the silver layer. Prior to applying the dielectric layer, an underlayer is applied over the silver layer. A barrier coating layer is applied over the fourth dielectric material layer in the coating stack. The barrier coating layer forms a region surrounded between the barrier coating layer and the substrate. Thus, the only oxygen that must be taken into account for the design of the coating laminate is, for example, the oxygen contained in the system when the coating laminate is formed as a result of depositing a dielectric layer by MSVD in an oxygen environment. It is. External oxygen is not relevant. This is because the covering laminate is an enclosed system.

As a result of the present invention, the underlying layer is the minimum thickness required to protect the degradable material, eg, the silver layer (s), while depositing the dielectric layer overlying it. Can be. In addition, a degradable material, such as silver layer (s), with a thinner substrate than currently taught in the art is required to bend the coated substrate to the desired contour or to strengthen the coated glass. Even during the heating process such as. This is because the surrounding O ₂ is limited to the system. As mentioned above, after heating, excess substrate can result in degradation at the interface of the individual coating layers.

  It has been found that the base layer can be as thin as 12 mm in the shape of the laminate. It is half the thickness required for similar coating shapes that must be able to withstand the deposition process and the heating conditions required to bend or strengthen the substrate without the use of a barrier coating layer.

  In the present invention, a thinner material can be used in the coated laminate described, so that a new material can be used as the underlayer. In particular, some materials could not be used conventionally. This is because in order to prevent the underlayers from being completely oxidized by heating, the underlayers must be made very thick, and there is a danger of forming an alloy with silver. Can be used. Such materials include, but are not limited to, aluminum, hafnium, and cobalt-chromium alloys.

  The present invention is illustrated by the following examples, but the invention is not limited thereto.

  FIG. 1 shows a heating study performed in the following manner. Glass substrates were prepared in the following manner: 3in x 6in x 0.08in clear float glass plates were coated with the coating upward on the conveyor belt of the product MSVD coater from Von Ardenne. . Two 3in × 3in × 0.08in transparent glass sheets were placed on the coated glass to cover the coating. The laminate was passed through a Lindberg furnace having 5 zones. Each region had a length of 10 inches. Described from the furnace inlet, the first zone is at a temperature of about 1350 ° F, the second zone is at a temperature of about 1130 ° F, the third zone is at a temperature of about 1180 ° F, and the fourth zone Was about 1205 ° F. and the fifth region was about 1195 ° F.

  As an example, the coated substrate was run through the furnace at various speeds. Upon exiting the furnace, the 3 in x 3 in glass sheet on the coated glass was removed and a 0.03 in thick polyvinyl butyral (PVB) sheet was placed over half of the coated glass substrate. The PVB was then covered with a single 3 × 3 × 0.09 in glass sheet removed previously to form a laminate covering half of the coated glass. The half laminated portion of the coated glass sheet was measured for visible light transmittance (LTA) using illumination A.

  It should be appreciated that the slower the belt speed, the longer the time during which the coated glass is exposed to furnace conditions and the coated substrate gets hotter. Belt speed is related to critical heat. In particular, the slower the belt speed, the longer the coating will be exposed to high temperatures and the greater the amount of critical heat that must be withstood for the coating to perform well.

  For thermal studies, all coatings were applied on 3 in x 6 in x 2.1 mm clear float glass sheets. Specification for an exemplary coated substrate is described below. A coated substrate designated as “3 × Ag (500)” was made in the following manner: a first layer of zinc stannate was applied on the substrate in a thickness of 390 mm; the first layer of zinc stannate A first layer of silver was applied at a thickness of 75 mm on the top; a first layer of titanium metal was applied on the first layer of silver at a thickness of 15 mm; over the first layer of titanium metal A second layer of zinc stannate was applied at a thickness of 690 ；; a second layer of silver was applied over the second layer of zinc stannate at a thickness of 75 ；; over the second layer of silver A second layer of titanium metal was applied to a thickness of 15 mm; a third layer of zinc stannate was applied to the second layer of titanium metal at a thickness of 690 mm; the third layer of zinc stannate A third layer of silver was applied at a thickness of 75 mm on the top; a third layer of titanium metal was applied on the third layer of silver at a thickness of 15 mm; over the third layer of titanium A fourth layer of zinc stannate was applied to a thickness of 390 mm; and a barrier coating composed of an alloy of alumina and silica was sputtered from a target comprising 60 wt% aluminum and 40 wt% silicon; A 500 Å thickness was applied over the fourth layer of dielectric material.

  A coated substrate designated as “3 × Ag (metal)” was made in the following manner: a first layer of zinc stannate was applied on the substrate in a thickness of 390 mm; A first layer of silver was applied at a thickness of 75 mm; a first layer of titanium metal was applied at a thickness of 15 mm on the first layer of silver; on the first layer of titanium metal; A second layer of zinc stannate was applied at a thickness of 690 mm; a second layer of silver was applied at a thickness of 75 mm on the second layer of zinc stannate; on the second layer of silver A second layer of titanium metal was applied at a thickness of 15 ；; a third layer of zinc stannate was applied at a thickness of 690 に over the second layer of titanium metal; A third layer of silver was applied at a thickness of 75 mm on top; a third layer of titanium metal was applied on the third layer of silver at a thickness of 15 mm; tin on the third layer of titanium Applying a fourth layer of zinc to have a thickness of 100 Å; applying a layer of titanium metal to a thickness of 26Å on the fourth layer of the zinc stannate.

  A coated substrate, designated as “2 × Ag (500)” was made in the following manner: a first layer of zinc stannate was applied on the substrate at a thickness of 390 mm; A first layer of silver was applied at a thickness of 75 mm; a first layer of titanium metal was applied at a thickness of 15 mm on the first layer of silver; on the first layer of titanium metal; A second layer of zinc stannate was applied at a thickness of 690 mm; a second layer of silver was applied at a thickness of 75 mm on the second layer of zinc stannate; on the second layer of silver A second layer of titanium metal was applied at a thickness of 15 mm; a third layer of zinc stannate was applied at a thickness of 390 mm on the second layer of titanium metal; and comprised of an alloy of alumina and silica The barrier coating layer formed was sputtered from a target containing 60% by weight aluminum and 40% by weight silicon to form a third layer of zinc stannate. It was applied at a thickness of 500Å on top of.

  A commercially available sample is included in FIG. In this sample, the glass substrate is a Sungate® automotive coating No. commercially available from PPG Industries, Pittsburgh, PA. 5 (SA05). SA05 is a double silver layer and heatable coating.

Conclusion As shown in the heating study of FIG. 1, the barrier coating of the present invention protects the degradable layer (s), thereby maintaining the performance of the coating. The coated substrates with 500 障壁 barrier coating layer according to the present invention: “3 × Ag (500)” and “2 × Ag (500)” maintained a fairly constant LTA regardless of belt speed. The sample designated as 3 × Ag (500) showed a decrease in LTA from 77% to 74% when the belt speed was reduced from 9 ipm to 3 ipm. The sample designated as 2 × Ag (500) showed a decrease in LTA from 76% to 72% when the belt speed was reduced from 9 ipm to 3 ipm. Since “3 × Ag (500)” and “2 × Ag (500)” include a 15 厚 thick underlayer, the decrease in LTA due to the decrease in belt speed is much less than expected.

  Substrates without the barrier coating according to the present invention showed a much worse decline for LTA with lower belt speeds than for substrates coated according to the present invention. The sample designated as 3 × Ag (metal) showed a decrease in LTA from 75% to 62% when the belt speed decreased from 9 ipm to 3 ipm. These results indicate that titanium does not have as good a barrier property as the barrier coating layer described in the present invention. Commercial samples show a decrease in LTA from 72% to 61% as the belt speed decreases from 9 ipm to 5 ipm, and then the LTA increases from 61% to 64% as the belt speed decreases from 5 ipm to 3 ipm did.

  Those skilled in the art will readily recognize that modifications can be made to the present invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the scope of the invention. Accordingly, the specific embodiments described in detail above are merely exemplary and are not limitations on the scope of the invention. The scope of the invention should be accorded the full scope of the appended claims and all equivalents thereto.

FIG. 1 shows a heating study performed on several coated substrates incorporating features of the present invention.

Claims (46)

A coating structure comprising a low emissivity functional coating comprising one or more metal-based coating laminate units and at least one barrier coating layer,
The barrier coating layer is disposed inside the low emissivity functional coating,
Each of the metal-based coated laminate units includes a first layer of dielectric material, a degrading layer of electromagnetic wave reflective material, an underlayer, and a second layer of dielectric material,
The coating structure according to claim 1, wherein the barrier coating layer includes at least one layer containing a mixture of aluminum oxide and silicon oxide.   The coating construction of claim 1, wherein the at least one barrier coating layer is a single layer.   The coating structure of claim 2, wherein the at least one barrier coating layer comprises a mixture of alumina and silica sputtered from a target comprising 60% aluminum and 40 wt% silicon.   The coating structure according to claim 2, wherein the at least one barrier coating layer has a thickness of up to 2 μ.   The at least one barrier coating layer is a multilayer coating comprising a first layer selected from silica, alumina, and mixtures thereof applied over a second layer comprising a mixture of silica and alumina. The coating structure according to 1.   The coating structure of claim 1, wherein the at least one degradable layer is an electromagnetic wave reflective material selected from gold, copper, silver, conductive nitride, and mixtures thereof.   The coating structure of claim 6, wherein the at least one degradable layer is silver.   The coating structure of claim 1, wherein the first and second dielectric material layers are each selected from indium tin oxide, titanium oxide, zinc oxide, tin oxide, mixtures and alloys thereof.   The coating structure of claim 1, wherein the first and second dielectric material layers each have a thickness in the range of 100 to 800 inches.   The coating structure according to claim 1, wherein the layer of the electromagnetic wave reflecting material has a thickness in the range of 50 to 300 mm.   The coating structure of claim 1, wherein the at least one underlayer has a thickness in the range of 10 to 30 mm.   At least one underlayer comprising titanium, copper, aluminum, niobium, yttrium, zirconium, hafnium, chromium, and mixtures and alloys thereof; nickel-chromium alloy; cobalt-chromium alloy; indium tin suboxide; titanium suboxide The coating structure of claim 11, selected from: zinc aluminum suboxide; silicon nitride; and mixtures thereof.   The coating structure of claim 6, wherein the degradable layer is a layer of conductive nitride.   The coating construction of claim 13, wherein the coating construction further comprises a transparent conductive oxide layer.   The at least one degradable layer is on at least a portion of the transparent conductive oxide layer, and the at least one barrier coating layer is on at least a portion of the at least one degradable layer. Coating structure.   15. The coating arrangement of claim 14, wherein a transparent conductive oxide layer is on at least a portion of at least one degradable layer and a barrier coating layer is on at least a portion of the transparent conductive oxide layer. body.   16. The coating structure of claim 15, wherein the transparent conductive oxide is selected from fluorine doped tin oxide, indium tin oxide, zinc aluminum oxide, and mixtures thereof.   The coating construction of claim 15, wherein the transparent conductive oxide layer has a thickness in the range of 1 to 2500 mm.   The coating structure of claim 15, wherein the conductive nitride layer is selected from titanium nitride, zirconium nitride, and mixtures thereof.   The coating structure of claim 15, wherein the conductive nitride layer has a thickness in the range of 10 to 500 inches.   The coating construction of claim 15, wherein the at least one barrier coating layer has a thickness of at least 100 mm. A coated substrate comprising a substrate and a low emissivity functional coating on at least a portion of the substrate,
The low emissivity functional coating comprises at least one barrier coating layer disposed inside the one or more metal-based coating stack unit and the low emissivity functional coating,
Each of the metal-based coated laminate units includes a first layer of a dielectric material, a degrading layer of an electromagnetic wave reflecting material, an underlayer, and a second layer of a dielectric material,
The coated substrate, wherein the barrier coating layer includes at least one layer containing a mixture of aluminum oxide and silicon oxide.   The coated substrate of claim 22, wherein the at least one barrier coating layer is a single layer.   24. The coated substrate of claim 23, wherein the at least one barrier coating layer comprises a mixture of alumina and silica sputtered from a target comprising 60 wt% aluminum and 40 wt% silicon.   23. A coated substrate according to claim 22, wherein the barrier coating layer has a thickness of up to 2 microns.   24. The coated substrate of claim 23, wherein the at least one degradable layer is an electromagnetic wave reflective material selected from gold, copper, silver, conductive nitride, and mixtures thereof.   27. A coated substrate according to claim 26, wherein the at least one degradable layer is silver.   The coated substrate of claim 22, wherein the first and second layers of dielectric material are each selected from indium oxide, titanium oxide, zinc oxide, tin oxide, and mixtures thereof.   The coated substrate of claim 22, wherein the first and second layers of dielectric material each have a thickness in the range of 100 to 800 inches.   23. A coated substrate according to claim 22, wherein the layer of electromagnetic wave reflecting material has a thickness in the range of 50 to 300 inches.   23. A coated substrate according to claim 22, wherein the at least one underlayer has a thickness in the range of 10 to 30 inches.   At least one underlayer comprising titanium, copper, aluminum, niobium, yttrium, zirconium, hafnium, chromium, and mixtures and alloys thereof; nickel-chromium alloy; cobalt-chromium alloy; indium tin suboxide; titanium suboxide 32. A coated substrate according to claim 31, selected from: zinc aluminum suboxide; silicon nitride; and mixtures thereof.   23. A coated substrate according to claim 22, wherein the at least one degradable layer is a layer of conductive nitride.   34. A coated substrate according to claim 33, wherein the coating structure further comprises a transparent conductive oxide layer.   35. The at least one degradable layer lies over at least a portion of the transparent conductive oxide layer, and the at least one barrier coating layer lies over at least a portion of the at least one degradable layer. Coated substrate.   36. The coated substrate of claim 35, wherein the transparent conductive oxide is selected from fluorine doped tin oxide, indium tin oxide, zinc aluminum oxide, and mixtures thereof.   36. The coated substrate of claim 35, wherein the transparent conductive oxide layer has a thickness in the range of 1 to 2500 mm.   35. The coated substrate of claim 34, wherein the conductive nitride layer is selected from titanium nitride, zirconium nitride, and mixtures thereof.   36. The coated substrate of claim 35, wherein the at least one degradable layer has a thickness in the range of 10 to 500 inches.   36. The coated substrate of claim 35, wherein the at least one barrier coating layer has a thickness of at least 100 inches.   The coated substrate of claim 22, wherein the substrate is selected from plastic, metal, ceramic, tile, glass, and combinations thereof.   42. A coated substrate according to claim 41, wherein the substrate is glass. A substrate;
A first layer of dielectric material comprising zinc stannate on the substrate;
A first degradable layer comprising silver on at least a portion of the first layer of dielectric material;
A first underlayer comprising titania over at least a portion of the first degradable layer;
A second layer of dielectric material comprising zinc stannate applied over at least a portion of the first underlayer;
A second degradable layer comprising silver over at least a portion of the second layer of dielectric material;
A second underlayer comprising titania over at least a portion of the second degradable layer;
A third layer of dielectric material comprising zinc stannate over at least a portion of the second underlayer;
A third degradable layer comprising silver over at least a portion of the third layer of dielectric material;
A third underlayer comprising titania over at least a portion of the third degradable layer;
A coating comprising: a fourth layer of dielectric material comprising zinc stannate on at least a portion of the third foundation layer; and at least one barrier coating layer comprising a mixture of alumina and silica and disposed in a coating laminate. A coated substrate comprising: a laminate.   44. The coated substrate of claim 43, wherein the first, second, third, and fourth layers of dielectric material have a thickness in the range of 100 to 800 inches.   44. The coated substrate of claim 43, wherein the first, second, and third underlayers have a thickness in the range of 10 to 18 inches.   44. The coated substrate of claim 43, wherein the first, second, and third degradable layers have a thickness in the range of 50 to 300 inches.

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